Process for separating tertiary monoolefins from non-tertiary mono-olefins



United States Patent 3,249,646 PROCESS FOR SEPARATING TERTIARY MONO- OLEFINS FROM NON-TERTIARY MONO-OLE FINS Stephen M. Kovach, St. Highland, Ind., assignor to Sinclair Research, Inc., Wilmington, Del., a corporation of Delaware No Drawing. Filed Dec. 11, 1962, Ser. No. 243,737 8 Claims. (Cl. 260-677) This invention relates to a process for the separation of primary and/or secondary monoolefins from a hydrophatic tertiary monoolefin hydrocarbons containing about 4 to 12, preferably 4 to 7, carbon atoms over defined catalysts while using particular processing con-ditions.

The separation of non-tertiary olefins from branched olefins is of vital interest to the petrochemical industry. Tertiary olefins are distinguished from non-tertiary olefins by having a tertiary carbon atom, that is a carbon atom attached to three other carbon atoms, with one of the three additional carbon atoms being the other carbon atom in the olefinic group. Non-tertiary olefins include primary, i.e. terminal olefins, and secondary olefins where each carbon atom of the olefinic group is attached to one other carbon atom. The process of the present invention provides a method of preparing substantially pure primary and secondary monoolefins, such as for instance, neo-olefins, i.e., olefins having a neo carbon atom and the unsaturation occurring in the terminal position of the carbon chain, e.g., 3,3-dimethyl butene-l, by the selective polymerization of the tertiary olefin admixed with the other olefins. Neo-acids and neo-alcohols have recently aroused much interest as components of synthetic lubricants having improved oxidation resistance and high temperature properties. Alternatively, the present invention provides a method wherein tertiary olefins are separated from the mixed olefinic hydrocarbon stream by polymerization of the tertiary olefin and a high purity tertiary olefin can be obtained by depolymerization of the polymerized tertiary olefin. Tertiary olefins, such as for instance, isobutene, branched amylenes, branched hexenes and branched heptenes are of current interest as raw materials for the synthesis of neo-acids and neo-alcohols. Tertiary olefins also are used in preparing alkylated phenols, such as tertiarybutyl phenol for use in modified phenol-formaldehyde resins. Branched amylenes, for example, are of importance as raw materials for the manufacture of isoprene, which is in turn used as a source of 'synthetic natural rubber. 3-methyl-l-butene which can be made from Z-methyl-Z-butene or 2-rnethyl-1-butene, is of interest as a monomer for the preparation of polymers. Isobutylene of high purity is desired for the manufacture of butyl rubber.

Neoolefins, such as neohexenes and neoheptenes, can be obtained through the condensation of t-butyl chloride with ethylene or propylene and dehydrochlorinating the resulting product to yield a crude product of neohexene or neoheptene containing unconverted halide plus monoand diisoolefins.- In the purification of neohexenes several fractionation towers are required to split the branched amylenes and isoprene from neohexene. Also, chemical treating such as low temperature acid extnaotion is required for removal of traces of isoprene branched amylenes in the neohexenes by polymerization. However, the

acid strength of the solid or liquid catalyst or the process conditions required to obtain conversion of the monoand 3,249,646 Patented May 3, 1966 "ice diisoolefins readily converts the neohexene through isomerization to -2,3-dimethylbutenes. At conditions where isomerization is negligible, the catalysts are inactive towards polymerization of the branched olefins. sulfuric acid can be utilized for adsorption of the monobranched olefins, but separation, washing, and corrosion problems are inherent with this separation technique. Likewise, branched olefins are needed in high purity for the production of polymers, alcohols, diolefins, etc. They may be extracted from mixed streams by fractionation, sulfuric acid extraction and azeotropic distillation, but these are costly means of separation. Fractionation is made difiicult by close boiling isomers and acid extraction may lead to dimerization and co-dimerization.

The present invention presents a process for the selective polymerization of branched olefins in admixture with primary and/or secondary monoolefins over a catalyst containing boria and alumina While employing a particular set of operating conditions. High conversions of the branched olefin to dimer, trimer, tetramer, pentamer, etc. isobtained with little or no primary monoolefin cOnVersion and relatively little secondary monoolefin reaction. If any branched diolefins are present, they will be polymerized whether they are conjugated or not. To obtain the desired results, it is important that the conditions of temperature and pressure employed in the process be such that the olefin remains essentially in the liquid phase. This necessitates maintaining processing temperatures below the critical temperature of the branched olefin and operating at pressures above the vapor pressure of the isoolefin at the processing temperature under essentially anhydrous conditions. Under these processing conditions carbon double bond and skeletal isomerization are substantially eliminated. In the polymerization convenient reaction temperatures are below about 200 F., for instance about 100 to 197 F., preferably about 80 to 150 F. for propylene; and the pressure often ranges from about 0 to 2000 p.s.i.g., preferably about atmospheric to "800 p.s.i.g. Space velocities in the range of about 0.1 to 20 LHSV (liquid hourly space velocity) have been found suitable but a space velocity of about 0. 1 to 10 LHSV is preferred. When using a boria-alumina catalyst, the principal products are the trimers, tetramers and pentamers of the tertiary olefin component of the feed. The polymer fraction can be separated from the unreacted olefins by any suitable means such as fractionation.

' The hydrocarbon stream can contain from'a'bout 10 to ferred to employ internal means as heat sinks. This can be accomplished for instance by employing inert hydrocarbon and catalyst diluents. The catalyst diluents are solid and the hydrocarbon diluents are liquid at the reaction conditions. The hydrocarbon diluent can be any hydrocarbon, unable to undergo polymerization, condenshould be non-alkylatable under the conditions utilized,

i.e., they sould be highly substituted as for instance tetra Dilute The inert 3 or higher substituted benzenes. The choice of solvent will depend on factors such as the olefiin feed, etc., which tend to maximize polymerization and minimize alkylation. Suitable inert catalyst diluents are any materials not sup- TABLE I [Catalyst: 10% BzO3/A1203. Conditions: Batch, F., 2113111., 60 min. porting the polymerization, e.g., tabular alumina, or 5 t n e, 88a feed,1-0id11uent] which would destroy the polymerization activity of the catalyst. The amount of liquid diluent may be present in Feed, Product, sthe range of about 0 to about or more, preferably about 0.5 to 2, volumes of diluent to about 1 volume of Light ends- 2. 8 0 100 the olefin. The solid diluent may be present in a volume 10 Neohexene 68.3 65 5 ratio of about 0 to about 10, preferably about 1 to 3, igfiggg T- g g fg k 3 63 volumes of the solid diluent to about 1 volume of the r n am boiling 0 100 e 8.2 catalyst. In addition, external sources of cooling may be f f Q 5 4 utilized such as circulating cold water, cold feed, air, etc. Polymer 0 16 18 The catlyst of the present invention is boria on alumina. s The boria iS present 011 the alumina support in catalytical- 1 Essentially tertiary olefins: Z-methyl-butene-l and lmethyl-butene-Z. Y e'fiectlve amounts- Generally thls amount W111 fan By distillation of the polymerization product a relatively Wlthln the range of abollt 2 to 20% by Welght: Preferably pure neohexene fraction is obtained, as shown in Table II. about 3 to 15% by weight. The catalyst support of the TABLE II present invention is an activated or a gamma-family 20 alumina e.g., gamma, eta., etc., such as those derived wtlpercent feed Wtpercent by calcination of amorphous hydrous alumina, alumina product; polymer monohydrate, alumina trihydrate or their mixtures. The free catalyst base most advantageous is derived from a mixture predominating, for instance, in about 65 to 9 5 weight perggggggg 2 3 cent, in one or more of the alumina trihydrates i.e., Branched amylones 9.1 4.4 bayerit e I, randomite (nordstrandite) or gibbsite, and alggi f ghig ggg gggf; Q3 0 so having about 5 to 35 weight percent of alumina mono- 2,3-dimethylbutene-1 0.6 5.4 hydrate (boehmite), amorphous hydrous alumina or their mixture. The alumina support can contain small amounts Thus, from Example I it is seenthat the light ends, of other materials, e.g., solid oxides such as silica, magthe unknown material in the same boiling range as the nesia, activated clays, titania, zirconia, etc. or their iSOPTeHe and isoprene have been stilectlvely Temovedmixtures Approximately two-thirds of the branched arnylenes conh catalysts can be prepared by impregnation using taining essentially tert ary olefins have been converted a water-soluble compound of the catalyst component. to h inner or h It IS also to be noted. that The boria can be added to the catalyst base in any stage abou; 2 :5 g ig neohexene was 150m of its preparation; however, it is frequently added to the er 126d to t e y catalyst after it has been formed by tabletting or extru- Example [I v sion and calcined. After the boria component addition, 40 A pentene Stream containing a Small amount of tertiary the catalyst can be calcined. A suitable water-soluble branched amylenes was processed in the liquid phase in bone p d 18 bone and runs 1 and 2 of Table III. In runs 3 and 4 a pentene To further llustrate the process of the present invenf d hi h in tertiary branched 'amylenes wasv processed t1011 the following eXamples are lllcllldedover a .boria-aluniina catalyst in the liquid phase. This Example I latter feed is representative of that available at a refinery and used in acid extraction processes for branched A crude neohexene (3,3-dimethyl-1-butene) fraction, amylene production, The processing gonditions and redescribed in Table I, was processed over a boria-alurnina s ilts obtained are presented in Table III..

TABLE III Ru'n No 1 l 2 3 4 5 c t 1 t s'o Y5 10% B Oa/Al Oa 3 5 41% i-C I Feed 11% s= :22 3%; 3- 25 i m, i165:

Conditions:

Temperature, F 0 0 40 200 Pressure, p.s.i.g Atin Atm. Atin Atm. Atm. LH Bate 2 Batch Batch 0.5 G. feed/g. cat. 0.9/1 3.5/1 1. 7/1 1.7/1 0. 5 Wt percent polym o 01 15 17 77 65 17 1435: 100 77 9s 42 11-0 4 9 43 21 12 G. i-O g. n-C 3/1 1/1 4/1 7/1 1/1. 5

1 Essentially tertiary branched amylencs.

2 Peut-ene-Z In Runs 1 and 2a near quantitative dimerization of the branched amy-lenes was obtained coupled with a very low co-dimerization 'of the normal pentenes, i.e., about 4%. In Runs 3 and 4 conversions and selectivities are good but processing in a batch operation lowered the selectivities probably due to the contact time with the catalyst. In runs 1 to 4 very little if any, double bond and skeletal isomerization occurred. Run S, employing a SiO -Al 0 catalyst, is presented to emphasize the superiority of the catalyst and processing conditions of the present invention in regard to conversion and selectivity. The branched amylene dimer can be utilized as gasoline or converted back to the isoamylene monomer by dedimerization, for instance by contacting the dimer at above room temperatures with acid catalysts.

The catalyst of the present invention possesses unique fouling and regenerating features. By operating at low temperatures this catalyst becomes deactivated not by carbon laydo-Wn on catalyst but loses activity by the plugging ofthe catalyst pores by heavy polymeric material. Polymerization activity can be restored, howvever, by Washing the catalyst with a suitable paraffin or aromatic hydrocarbon solvent as, for instance, n-pentane or benzene. If solvent washing fails, reactivation can be brought about by heat-treating the catalyst to 400 to 700 F. and purging with an inert gas such as nitrogen. This high temperature purge drives the heavy polymeric material out of the pores of the catalyst depositing only a small amount of carbon on the catalyst without loss in polymerization activity. In addition, catalyst reactivation can be accomplished by employing a hydrogenation metal component on the catalyst, e.g. a platinum group or iron group metal and hydrogenating the adsorbed polymer to a paraflin which is readily desorbed.

It is claimed:

1. A process for the selective separation of C to C tertiary monoolefin hydrocarbons from admixture with non-tertiary monoolefin hydrocarbons of approximately the same boiling range which consists essentially of contacting a mixture of said tertiary and non-tertiary monoolefin hydrocarbons with a catalyst consisting essentially of a catalytic amount of boria supported on activated alumina at a contact temperature and pressure suflicient to maintain said mixture essentially in the liquid phase, said temperature being from about -100 to 200 F. and said pressure being from about 0 to 2000 p.s.i.g., to selectively'polymerize said tertiary olefin, and separating the resulting tertiary olefin polymer from the polymerization product.

2. The process of claim 1 wherein the contact tempera- 6 ture is about to 150 F. and the contact pressure is about atmospheric to 800 p.s.i.g.

3. The method of claim 2 wherein the feed contains a primary monoolefin selected from a group consisting of neohexene and pentene.

4. The method of claim 2 wherein the amount of boria on the alumina support is about 3 to 15% by weight.

5. The process of claim 2 wherein the space velocity is about 0.1 to 10 LHSV.

6. The process of claim 1 wherein the space velocity is from about 0.1 to 20 LHSV.

7. A process for the purification of a crude neohexene fraction containing as impurities tertiary amy'lenes and isoprene which consists essentially of contacting said crude fraction in the liquid phase with a catalyst consisting essentially of a catalytic amount of boria supported on activated alumina at a contact temperature of from about to 200 F., contact pressure of from about 0 to 2000 p.s.i.g. and space velocity of from about 0.1 to 20 LHSV, said temperature and pressure being eifective to maintain said mixture in" the liquid phase, whereby to selectively polymerize said impurities, and thereafter separating neohexene in the polymerization product from the selectively polymerized impurities.

8. A process for the purification of a crude pentene fraction containing as impurities tertiary amylene which consists essentially of contacting said crude fraction in the liquid phase with a catalyst consisting essentially of a catalytic amount of boria supported on activated alumina at a contact temperature of from about 100 to 200 F., contact pressure of from about 0 to 2000 p.s.i.g. and space velocity of from about 0.1 to 20 LHSV, said temperature and pressure being effective to maintain said mixture in the liquid phase, whereby to selectively polymerize said impurities, and thereafter separating pentene in the polymerization product from the selectively polymerized impurities.

References Cited by the Examiner UNITED STATES PATENTS 2,007,160 7/1935 Engs et a1 260677 2,301,342 11/1942 Sumerford et al. 260683.2 2,342,074 2/ 1944 Deanesly et al. 260-677 2,414,760 1/ 1947 'Mottern 260677 2,552,692 5/1951 Schulze et a1 260677 2,989,574 6/1961 Pfefferle et al. 260-683.44 3,086,066 4/ 1963 Breiter et al 260677 ALPHONSO D. SULLIVAN, Primary Examiner.

D. S. ABRAMS, Assistant Examiner. 

1. A PROCESS FOR THE SELECTIVE SEPARATION OF C4 TO C12 TERTIARY MONOOLEFIN HYDROCARBONS FROM ADMIXTURE WITH NON-TERTIARY MONOOLEFIN HYDROCARBONS OF APPROXIMATELY THE SAME BOILING RANGE WHICH CONSISTS ESSENTIALLY OF CONTACTING A MIXTURE OF SAID TERTIARY AND NON-TERTIARY MONOOLEFIN HYDROCARBONS WITH A CATALYST CONSISTING ESSENTIALLY OF A CATALYTIC AMOUNT OF BORIA SUPPORTED ON ACTIVATED ALUMINA AT A CONTACT TEMPERATURE AND PRESSURE SUFFICIENT TO MAINTAIN SAID MIXTURE ESSENTIALLY IN THE LIQUID PHASE, SAID TEMPERATURE BEING FROM ABOUT -100 TO 200*F. AND SAID PRESSURE BEING FROM ABOUT 0 TO 2000 P.S.I.G., TO SELECTIVELY POLYMERIZE SAID TERTIARY OLEFIN, AND SEPARATING THE RESULTING TERTIARY OLEFIN POLYMER FROM THE POLYMERIZATION PRODUCT. 